Process for producing a hydrodesulfurization catalyst

Abstract: A process for producing a hydrodesulfurization catalyst is disclosed, comprising impregnating an inorganic oxide carrier containing a crystalline aluminosilicate with a solution consisting of Group VI metal oxide, a Group VIII metal oxide, and phosphorus. Also disclosed is a process for deep hydrodesulfurization of a gas oil fraction using said catalyst to obtain gas oil having an extremely low sulfur content.

Description: FIELD OF THE INVENTION This invention relates to a process for producing a catalyst for hydrodesulfurization of hydrocarbon oils More particularly, it relates to a process for producing a catalyst for hydrodesulfurization, which catalyst contains a large amounts of a Group VIB metal, a Group VIII metal and phosphorus. BACKGROUND OF THE INVENTION Hydrocarbon oils generally contain sulfur compounds. When a hydrocarbon oil is used as fuel, sulfur in the sulfur compounds is converted to sulfur oxides, which are discharged into the atmosphere. In order to reduce air pollution caused by combustion of a hydrocarbon oil, it is desirable to reduce the sulfur content of a hydrocarbon oil to as low a level as possible. This can be achieved by subjecting the hydrocarbon oil to a catalytic hydrodesulfurization process (HDP). Catalysts conventionally used for HDP comprise an oxide carrier, such as alumina, magnesia or silica, supported thereon a metal belonging to Group VIB of the Periodic Table (hereinafter simply referred to as a Group VIB metal) and a metal belonging to Group VIII of the Periodic Table (hereinafter simply referred to as a Group VIII metal) as active metals. Mo or W is normally used as the Group VIB metal, and Co or Ni is normally used as the Group VIII metal. Addition of phosphorus, boron, etc. to the catalyst has been proposed for improvement of catalytic activity as disclosed in JP-A-52-13503 (the term "JP-A" as used herein means an "unexamined published Japanese patent application). On the other hand, incorporation of crystalline aluminosilicate into an inorganic oxide carrier is disclosed in JP-A-56-20087. A combination of these techniques is also disclosed in JP-A-61-126196 and JP-A-2-214544. Conventional methods for incorporating the above-mentioned active metal into a carrier include a so-called impregnation process using an aqueous impregnating solution of a salt of the metal, such as an ammonium salt or a nitrate. Where phosphorus is also to be supported, however, it has been difficult to prepare a catalyst having high contents of a Group VIB metal and phosphorus through one-step impregnation on account of relatively low solubility of a Group VIB metal salt into a phosphoric acid solution. Therefore, the impregnation had to be performed in two steps; a carrier is impregnated first with phosphorus and then with a Group VIB metal. Otherwise, the amount of the Group VIB metal to be supported had to be reduced to undesirable level. According as the restriction on sulfur content in gas oil products available on the market is raised for environmental conservation (e.g., the upper limit of 0.5% by weight was lowered to 0.05% by weight), deeper desulfurization is being mandatory, and it has been demanded to establish a technique for removing sulfur-containing compounds which are hardly desulfurized (hereinafter referred to as intractable substances), such as 4-methyldibenzothiophene (4M-DBT) and 4,6-dimethyldibenzothiophene (4,6DM-DBT). Under these circumstances, JP-A-4-265158 discloses a process for obtaining a catalyst containing more than 20% by weight of a Group VIB metal in combination with phosphorus through a single impregnation step. However, the process disclosed needs a considerably high temperature and a long time for preparing an impregnating solution, which has disadvantage for mass production. The above-mentioned incorporation of crystalline aluminosilicate into an inorganic oxide carrier is aimed at obtaining light oil by cracking of heavy oil and has not been employed for deep desulfurization of a light oil fraction. US-4 089 775 relates to a process for simultaneously desulfurizing and dewaxing raw, untreated, high sulfur-containing wide-cut petroleum oil fractions. Catalysts useful for this purpose are low sieve-content catalysts comprising a mixture of a major amount of an amorphous component and minor amounts of (1) faujasite and (2) a hydrogenation component comprising one or more transitional metals selected from Groups VIB and/or VIII of the Periodic Table and the oxides and sulfides thereof. The catalyst may be prepared by impregnating the silica/alumina support with nickel and molybdenum, forming a slurry of the impregnated support and mixing the faujasite into the slurry which is then extruded and dried. JP-62/107150 relates to a catalyst with enhanced hydrodesulfurization/ hydrodenitrification activity which is obtained by supporting a specific amount of metals of the Group VIa and Group VIII of the Periodic Table and phosphorus on an alumina carrier of which the pore distribution and average pore size takes specific range values. SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing a catalyst exhibiting excellent hydrodesulfurization activity in deep desulfurization of gas oil. Another object of the present invention is to provide a process for producing a catalyst for hydrodesulfurization in which a carrier can be impregnated with a Group VIB metal, a Group VIII metal, and phosphorus at one time to high contents at a low temperature in a short time. The present invention relates to a process for producing a catalyst for hydrodesulfurization of hydrocarbon oils comprising impregnating an inorganic oxide carrier containing a crystalline aluminosilicate with an impregnating solution consisting of a polyacid salt of a metal belonging to Group VIB of the Periodic Table, a salt of a metal belonging to Group VIII of the Periodic Table, and phosphoric acid to provide a Group VIB metal content of from 10 to 30% by weight, a Group VIII metal content of from 1 to 15% by weight, and a phosphorus content of from 0.1 to 15% by weight each in terms of oxide with respect to the total catalyst, drying the impregnated carrier, and calcining said carrier, wherein said inorganic oxide is selected from silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia and combinations of two or more thereof. DETAILED DESCRIPTION OF THE INVENTION The carrier which can be used in the present invention is an inorganic oxide containing a crystalline aluminosilicate. The inorganic oxides are selected from silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia, with alumina, silica-alumina, alumina-titania, alumina-boria, and alumina-zirconia being preferred. Alumina is preferably γ-alumina. These inorganic oxides can be used either individually or in combination of two or more thereof. The crystalline aluminosilicate preferably having a unit cell dimension between 24.45 Å and 24.55 Å which is incorporated into the inorganic oxide includes A type zeolite, X type zeolite, Y type zeolite, stabilized Y type zeolite, superstabilized Y type zeolite, HY type zeolite, L type zeolite, and ZSM type zeolite, with HY type zeolite and stabilized Y type zeolite being preferred. These crystalline aluminosilicates can be used either individually or in combination of two or more thereof. Zeolite whose unit cell dimension is less than 24.45 Å, although having a high total amount of acidic sites, exhibits insufficient acid strength for removing intractable substances at commonly employed desulfurization temperatures. On the other hand, zeolite whose unit cell dimension exceeds 24.55 Å has an insufficient total amount of acidic sites, only exhibiting low activity as a whole. The carrier preferably consists of 80 to 99% by weight, more preferably 85 to 98% by weight, of an inorganic oxide and 1 to 20% by weight, more preferably 2 to 15% by weight, of zeolite. If the proportion of the inorganic oxide in the carrier is less than 80% by weight, the surface area of the catalyst is insufficient. Besides, zeolite, if present in a proportion of more than 20% by weight, may deteriorate degree of dispersion in respect of active metal components. If the proportion of the inorganic oxide exceeds 99% by weight, i.e., if the proportion of zeolite is less than 1% by weight, there may be no technical significance of incorporating zeolite. If desired, the carrier may further contain one or more of clay minerals, such as montmorillonite, kaoline, halloysite, bentonite, attapulgite, bauxite, kaolinite, nacrite, and anorthite. While not limiting, the carrier preferably has a specific surface area of not less than 250 m 2 /g (measured by a BET method) for accomplishing the objects of the present invention, i.e., to impregnate a carrier with a Group VIB metal, a Group VIII metal, and phosphorus to high contents at a low temperature in a short time to provide a catalyst exhibiting excellent hydrodesulfurization activity in deep desulfurization. For the same reason, the carrier, while not limiting, preferably has a pore volume between 0.3 cc/g and 1.2 cc/g and a mean pore diameter between 50 Å and 130 Å. Inorganic polyacid salts of Group VI metals which can be supported on the above-mentioned carrier preferably include those of chromium, molybdenum or tungsten, still preferably heteropoly-acid salts of molybdenum or tungsten. Examples of useful inorganic heteropoly-acids are phosphomolybdic acid [H 3 (PMo 12 O 40 )·30H 2 O], silicomolybdic acid [H 3 (SiMo 12 O 40 )·30H 2 O], phosphotungstic acid [H 3 (PW 12 O 40 )·30H 2 O], and silicotungstic acid [H 3 (SiW 12 O 40 )·30H 2 O]. Preferred of them are phosphomolybdic acid and silicomolybdic acid, with phosphomolybdic acid being still preferred. These polyacid salts can be used either individually or in combination of two or more thereof. The Group VIII metal salts which can be supported on the carrier together with the above-mentioned Group VIB metal polyacid salt include salts of iron, cobalt, nickel, rhodium, palladium, osmium, iridium or platinum, with a carbonate, an acetate or a phosphate of cobalt or nickel being preferred. These metal salts can be used either individually or in combination of two or more thereof. Phosphoric acid which can be supported on the carrier together with the Group VIB metal polyacid salt and the Group VIII metal salt includes orthophosphoric acid, metaphosphoric acid, pyrrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and polyphosphoric acid, with orthophosphoric acid being preferred. The above-mentioned Group VIB metal component, Group VIII metal component, and phosphorus (hereinafter inclusively referred to as catalyst components) are incorporated into the aforesaid carrier in a conventional manner. Known techniques for incorporating catalyst components into a carrier which may be applied to the production of the catalyst of the present invention include impregnation comprising impregnating a carrier with an impregnating solution having dissolved therein the catalyst components; spraying consisting of spraying the impregnating solution onto the carrier; chemical vapor deposition consisting of chemically depositing the catalyst components on the carrier; a so-called kneading process in which the above-described carrier components are kneaded with a part or the whole of the catalyst components and then molded into a carrier; a so-called coprecipitation process; and a so-called alkoxide process. The solvent for dissolving the catalyst components to prepare an impregnating solution which can be used in the above-mentioned impregnation process is not particularly limited and includes, for example, water, alcohols, ethers, ketones, and aromatic solvents. Examples of suitable solvents are water, acetone, methanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, hexanol, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, and dioxane. Preferred of them is water. The proportions of the catalyst components in the impregnating solution are usually selected so that the catalyst after calcination may contain from 10 to 30% by weight, preferably from 18 to 25% by weight, in terms of oxide, of the Group VIB metal and from 1 to 15% by weight, preferably from 3 to 7% by weight, in terms of oxide, of the Group VIII metal with respect to the total catalyst. If the amount of the Group VIB metal polyacid salt in the solution is less than what would provide 10% by weight of the Group VIB metal oxide in the catalyst, the Group VIII metal salt tends to become hard to dissolve in the solution. If the content of the Group VIB metal in the catalyst exceeds 30% by weight in terms of oxide, the surface area of the catalyst tends to be decreased to reduce the catalytic activity. If the content of the Group VIII metal salt in the catalyst is less than 1% by weight in terms of oxide, sufficient catalytic activity cannot be obtained. If it exceeds 15% by weight, the oxide of the metal is apt to cover the whole surface of the catalyst to reduce the catalytic activity. The proportion of phosphoric acid in the solution is selected so that the catalyst after calcination may have a phosphorus content of from 0.1 to 15% by weight, preferably from 1 to 7% by weight, in terms of oxide. If the proportion of phosphoric acid is too low, no significant technical effect is produced by addition of phosphoric acid. If it is too high, there is a tendency that the resulting catalyst has a reduced pore volume, leading to reduction in catalytic activity. The solvent is normally used in an amount of from 50 to 150 g, preferably from 70 to 90 g, per 100 g of the carrier. Too small an amount of the solvent fails to be sufficiently infiltrated into the carrier. If the amount of the solvent is too large, the dissolved active metal components cannot be infiltrated into the carrier, rather adhering to the inner wall of an impregnating container, failing to assure desired contents of the catalyst components. An impregnation solution can be prepared by dissolving the catalyst components at a temperature higher than 0°C and lower than 100°C. Within this temperature range, the catalyst components can satisfactorily be dissolved in the solvent. The thus prepared impregnating solution is infiltrated into the carrier to support the catalyst components in the solution on the carrier through one impregnation step, and the impregnated carrier is dried and calcined to obtain the catalyst to be used in the present invention. If desired, impregnation of the three catalyst components may be carried out through two divided stages. In this case, the impregnated carrier may be dried and calcined between two impregnation stages. For example, in a preferred embodiment of impregnation, the catalyst of the present invention can be prepared by impregnating the carrier first with an impregnating solution containing the Group VIB metal polyacid salt and phosphoric acid to support 10 to 30% by weight of the Group VIB metal and 0.1 to 15% by weight of phosphorus each in terms of oxide based on the catalyst, drying, calcining, then impregnating the calcined carrier with a second impregnating solution containing the Group VIII metal salt to support 1 to 15% by weight, in terms of oxide, of the Group VIII metal based on the catalyst, followed by drying and calcining. Impregnation can be carried out under various conditions, usually at a temperature higher than 0°C and lower than 100°C, preferably from 10 to 50°C, still preferably from 15 to 30°C, for a period of from 15 minutes to 3 hours, preferably from 20 minutes to 2 hours, still preferably from 30 minutes to 1 hour. At too high an impregnating temperature, the solution undergoes drying during impregnation, resulting in localization of the catalyst components. It is preferable to agitate the solution and carrier during impregnation. Drying of the impregnated carrier can be performed by various drying methods, such as air drying, hot air drying, heat drying, and freeze-drying. Calcination can be conducted by means of various furnaces, such as an electric oven, a muffle furnace, an alundum bath, and an electric tubular furnace. It is usually preferable to carry out calcination in an electric oven under aeration or in a muffle oven. The calcining temperature is selected appropriately according to the calcination method used. For example, calcination in an electric oven under aeration or in a muffle oven is effected at 200 to 800°C, preferably 300 to 700°C, still preferably 450 to 650°C. If the calcining temperature is too low, the active metal components cannot be supported sufficiently, and catalyst poison remains. If it is too high, the catalyst undergoes sintering. The calcination time is preferably 2 to 10 hours, still preferably 3 to 5 hours. It is preferable, while not essential, for efficient removal even of intractable substances that the thus prepared catalyst of the present invention has a specific surface area of not less than 200 m 2 /g and a pore volume of from 0.3 to 1.2 cc/g. Further, the catalyst suitably has a mean pore diameter of from 70 to 80 Å, preferably from 73 to 77 Å. A catalyst with too large a mean pore diameter facilitates diffusion of a reactant therathrough but has a reduced effective surface area, making it difficult to remove intractable substances. In the case of deep desulfurization, it is a practice often followed to conduct the reaction at a decreased liquid hourly space velocity so as to reduce the sulfur content to a prescribed level without deteriorating the color of the resulting gas oil. This being the case, the contact time would be extended so that there is no need any more to improve diffusion of a reactant by making the mean pore diameter larger. Moreover, no improvement in activity is observed with use of such a catalyst having a large mean pore diameter. On the other hand, a catalyst having too small a mean pore diameter encounters difficulty in production. For example, the physical properties essential for functioning as a catalyst (i.e., specific surface area and pore volume) could not be assured without involving the sacrifice of mechanical strength. The pore size distribution is preferably 70% or more, still preferably 80% or more, as expressed in terms of a proportion of those pores having a pore size of the mean pore diameter ± 15 Å. If the pore size distribution is too small, i.e., showing a broad distribution curve, the number of the effective pores becomes relatively small even if the mean pore diameter is in an ideal range, failing to meet the expectation. The catalyst is not particularly limited in shape and may have any shape usually used in this kind of catalysts, for example, a cylindrical or four-leaf form. A suitable size of the catalyst is usually 0,25 to 0,11 cm (1/10 to 1/22 in.) in diameter and 8 to 9 cm (3.2 to 3.6 in.) in length. The catalyst of the present invention may be used either alone or, if desired, as a mixture with a known catalyst or a known inorganic oxide carrier in the use thereof. If desired, the catalyst of the present invention may further be formed in combination with one or more of clay minerals, such as montmorillonite, kaoline, halloysite, bentonite, attapulgite, bauxite, kaolinite, nacrite, and anorthite. Starting oils which can be hydrodesulfurized according to the present invention include gas oil obtained by catalytic cracking or thermal cracking, straight-run gas oil, coker gas oil, gas oil having been subjected to a hydrogenation treatment, and gas oil having been subjected to a desulfurization treatment. They may be used either individually or in combination of two or more thereof. Oils suitable to be treated have a boiling point ranging from 150 to 400°C, preferably from 200 to 380°C, still preferably from 220 to 340°C, and a sulfur content of not more than 3% by weight, preferably not more than 2.5% by weight, still preferably not more than 2.0% by weight. The catalytic hydrodesulfurization reaction is usually carried out under a hydrogen partial pressure of from 30 to 80 kg/cm 2 , preferably 50 to 60 kg/cm 2 ; at a temperature of from 320 to 380°C, preferably 320 to 360°C, more preferably 330 to 360°C; at a liquid hourly space velocity (LHSV) of from 1.0 to 5.0 hr -1 , preferably 1.0 to 3.0 hr -1 , more preferably 1.0 to 2.0 hr -1 ; and at a hydrogen/oil ratio of from 100 to 400 ℓ/ℓ, preferably 200 to 300 ℓ/ℓ. Under a hydrogen pressure lower than 30 kg/cm 2 , intractable substances could not be removed. If the hydrogen pressure exceeds 80 kg/cm 2 , not only would the removal efficiency of intractable substances reach saturation but a pressure-resistant and expensive apparatus would be required to increase the cost. If the reaction temperature is lower than 320°C, intractable substances cannot be removed. Even if it exceeds 380°C, the removal efficiency of intractable substances is saturated only resulting in uneconomical choice. If the liquid hourly space velocity exceeds 5.0 hr -1 , the contact time between the catalyst and the oil is insufficient for removal of intractable substances. If it is less than 1.0 hr -1 , the contact time will be increased more than necessary, resulting in reduction of feed capacity. From the viewpoint of sulfur content of product oils, it is recommended to decide the reaction conditions so that the resulting product oil may have a sulfur content in the range of from 0.001 to 0.10% by weight, preferably from 0.005 to 0.05% by weight, still preferably from 0.01 to 0.03% by weight. Under so selected reaction conditions, the working life of the catalyst according to the present invention is equal or even longer than that of typical conventional catalysts. In other words, it is possible to use the catalyst of the present invention in an industrial apparatus for at least one year. In a process operated on a commercial scale, the catalyst is used in an appropriate reactor in the fixed bed, moving bed or fluidized bed form with respect to the catalyst particles, and the oil to be desulfurized is charged into the reactor and treated under predetermined conditions. In a general embodiment, the catalyst is maintained in the fixed bed form and the oil is allowed to pass therethrough downward. The catalyst may be used in a single reactor, or may be distributed in two or more reactors connected in series. The present invention will now be illustrated in greater detail by referring to the following Examples, but it should be understood that the present invention is not to be construed as being limited thereto. All the percents are by weight unless otherwise indicated. EXAMPLE 1 An impregnating aqueous solution was prepared by dissolving 11 g of cobalt carbonate, 4 g of phosphoric acid, and 38 g of phosphomolybdic acid [H 3 (PMo 12 O 40 )·30H 2 O] in 75 g of water with stirring in an Erlenmeyer flask at room temperature. The aqueous solution was infiltrated into 100 g of an alumina carrier containing 5% of HY type zeolite (specific surface area: 372 m 2 /g; pore volume: 0.65 cc/g; substantially made of γ-alumina) in an egg-plant type flask at room temperature for 1 hour. The impregnated carrier was air dried and calcined at 500°C for 4 hours in a muffle furnace to obtain a catalyst (hereinafter designated catalyst A). EXAMPLE 2 Catalyst B was prepared in the same manner as in Example 1, except for replacing 11 g of cobalt carbonate with 11 g of nickel carbonate. EXAMPLE 3 Catalyst C was prepared in the same manner as in Example 1, except for replacing 38 g of phosphomolybdic acid with 36 g of phosphotungstic acid [H 3 (PW 12 O 40 )·30H 2 O]. EXAMPLE 4 Catalyst D was prepared in the same manner as in Example 1, except for changing the amount of phosphomolybdic acid to 28.5 g. EXAMPLE 5 Catalyst E was prepared in the same manner as in Example 1, except for changing the amount of phosphomolybdic acid to 47.5 g. EXAMPLE 6 Catalyst F was prepared in the same manner as in Example 1, except for changing the amount of phosphoric acid to 6.2 g. EXAMPLE 7 Catalyst G was prepared in the same manner as in Example 1, except for changing the HY type zeolite content in the alumina carrier to 10%. EXAMPLE 8 Catalyst H was prepared in the same manner as in Example 1, except for changing the HY type zeolite content in the alumina carrier to 20%. EXAMPLE 9 Catalyst I was prepared in the same manner as in Example 3, except for replacing 11 g of cobalt carbonate with 11 g of nickel carbonate. EXAMPLE 10 Catalyst J was prepared in the same manner as in Example 1, except for changing the amount of cobalt carbonate to 15.4 g. EXAMPLE 11 Catalyst K was prepared in the same manner as in Example 1, except for changing the amount of cobalt carbonate to 8.8 g. EXAMPLE 12 Catalyst L was prepared in the same manner as in Example 1, except for replacing 11 g of cobalt carbonate with 21.6 g of cobalt acetate. COMPARATIVE EXAMPLE 1 In an Erlenmeyer flask, 32.7 g of ammonium molybdate was dissolved in 75 g of water at room temperature. Aqueous ammonia was added thereto with stirring until the ammonium molybdate was completely dissolved to prepare a first impregnating solution. The aqueous solution was infiltrated into 100 g of a γ-alumina carrier having a specific surface area of 336 m 2 /g, a pore volume of 0.71 cc/g, and a mean pore diameter of 85 Å in an egg-plant type flask at room temperature for 1 hour. The impregnated carrier was air dried and calcined at 500°C for 4 hours in a muffle furnace. Separately, 26 g of cobalt nitrate was dissolved in 70 g of water with stirring at room temperature in a Erlenmeyer flask to prepare a second impregnating solution. The above obtained catalyst was impregnated with the second impregnating solution at room temperature for 1 hour in an egg-plant type flask, dried, and calcined in the same manner as described above to obtain catalyst M. COMPARATIVE EXAMPLE 2 Catalyst N was prepared in the same manner as in Example 1, except for using the same γ-alumina as used in Comparative Example 1 as a carrier. COMPARATIVE EXAMPLE 3 Catalyst O was prepared in the same manner as in Comparative Example 1, except for using the same HY type zeolite-containing alumina as used in Example 1 as a carrier. COMPARATIVE EXAMPLE 4 Catalyst P was prepared in the same manner as in Example 1, except for changing the amount of phosphomolybdic acid to 15.2 g. COMPARATIVE EXAMPLE 5 Catalyst Q was prepared in the same manner as in Example 1, except for changing the amount of phosphoric acid to 19.4 g. COMPARATIVE EXAMPLE 6 In an Erlenmeyer flask, 4.2 g of phosphoric acid was dissolved in 75 g of water with stirring at room temperature to prepare a first impregnating solution. The first impregnating solution was infiltrated into 100 g of the same carrier as used in Example 1 in an egg-plant type flask at room temperature for 1 hour. The impregnated carrier was air dried and calcined at 500°C for 4 hours in a muffle furnace. Separately, 32.7 g of ammonium molybdate was dissolved in 65 g of water with stirring at room temperature in an Erlenmeyer flask to prepare a second impregnating solution. The above obtained catalyst was impregnated with the second impregnating solution at room temperature for 1 hour in an egg-plant type flask, dried, and calcined in the same manner as described above. A third impregnating solution was prepared by dissolving 26 g of cobalt nitrate in 60 g of water in an Erlenmeyer flask at room temperature while stirring. The above prepared catalyst was impregnated with the third impregnating solution at room temperature in an egg-plant type flask, dried, and calcined in the same manner as described above to obtain catalyst R. COMPARATIVE EXAMPLE 7 In an Erlenmeyer flask, 32.7 g of ammonium molybdate was dissolved in 75 g of water at room temperature while stirring to prepare a first impregnating solution. The first impregnating solution was infiltrated into 100 g of the same carrier as used in Example 1 at room temperature for 1 hour in an egg-plant type flask. The impregnated carrier was air dried and calcined at 500°C for 4 hours in a muffle furnace. Separately, 4.2 g of phosphoric acid and 26 g of cobalt nitrate were dissolved in 70 g of water with stirring at room temperature in an Erlenmeyer flask to prepare a second impregnating solution. The above obtained catalyst was impregnated with the second impregnating solution at room temperature in an egg-plant type flask, dried, and calcined in the same manner as described above to obtain catalyst S. COMPARATIVE EXAMPLE 8 In an Erlenmeyer flask, 32.7 g of ammonium molybdate, 26 g of cobalt nitrate, and 4.2 g of phosphoric acid were stirred in 75 g of water at room temperature in an attempt to prepare an impregnating solution that would provide 3.0% of CoO, 20.0% of MoO 3 and 3.0% of P 2 O 5 in the whole composition of a calcined catalyst. However, insoluble matter remained in the solution, therefore the solution was unsuitable as an impregnating solution. It is thus seen that use of a compound of a Group VIB metal like ammonium molybdate, that has typically been employed, fails to provide a desired phosphorus content and a desired Group VI metal content. The composition and properties of catalysts A to S obtained in Examples 1 to 12 and Comparative Examples 1 to 7 and catalyst A1 prepared in Example 14 hereinafter described are shown in Tables 1 and 2, respectively. Example No. Group VIII Metal Oxide Group VI Metal Oxide Catalyst Amount (wt%) Amount (wt%) P 2 O 5 (wt%) Zeolite (wt%) Example 1 CoO 5 MoO 3 20 3 5 A 2 NiO 5 MoO 3 20 3 5 B 3 CoO 5 WO 3 20 3 5 C 4 CoO 5 MoO 3 15 3 5 D 5 CoO 5 MoO 3 25 3 5 E 6 CoO 5 MoO 3 20 5 5 F 7 CoO 5 MoO 3 20 5 10 G 8 CoO 5 MoO 3 20 5 20 H 9 NiO 5 WO 3 20 3 5 I 10 CoO 7 MoO 3 20 3 5 J 11 CoO 3 MoO 3 20 3 5 K 12 CoO 5 MoO 3 20 3 5 L Compara. Example 1 CoO 5 MoO 3 20 - - M 2 CoO 5 MoO 3 20 3 - N 3 CoO 5 MoO 3 20 - 5 O 4 CoO 5 MoO 3 8 3 5 P 5 CoO 5 MoO 3 20 16 5 Q 6 CoO 5 MoO 3 20 3 5 R 7 CoO 5 MoO 3 20 3 5 S Example 14 CoO 5 MoO 3 20 3 5 A1 Example No. Specific Surface Area (m 2 /g) Pore Volume (cc/g) Mean Pore Diameter (Å) Catalyst Example 1 262 0.44 82 A 2 271 0.43 76 B 3 254 0.45 77 C 4 280 0.46 75 D 5 243 0.41 79 E 6 258 0.40 84 F 7 276 0.41 76 G 8 309 0.39 79 H 9 260 0.42 77 I 10 247 0.40 75 J 11 283 0.45 78 K 12 276 0.44 76 L Compara. Example 1 284 0.56 75 M 2 249 0.42 81 N 3 297 0.62 76 O 4 281 0.46 78 P 5 170 0.28 94 Q 6 211 0.45 77 R 7 240 0.40 79 S Example 14 247 0.41 84 A1 EXAMPLE 13 Each of catalysts A to S prepared in Examples 1 to 12 and Comparative Examples 1 to 4, 6, and 7 and catalyst A1 prepared in Example 14 hereinafter described was used for hydrodesulfurization of gas oil having a specific gravity (15/4°C) of 0.851, a sulfur content of 1.35%, a nitrogen content of 20 ppm, and a viscosity (30°C) of 5.499 cSt under the following reaction conditions. Prior to use, each catalyst was activated under the following conditions. Catalyst Q obtained in Comparative Example 5 had poor activity due to a small pore volume and a small specific surface area and was not tested. Conditions of Hydrodesulfurization: Temperature: 340°C Hydrogen pressure: 35 kg/cm 2 LHSV: 1.5 or 4.2 hr -1 Apparatus: Fixed-bed type high pressure flow reactor Conditions of Activation of Catalyst: Pressure: 35 kg/cm 2 Atmosphere: Hydrogen sulfide/hydrogen mixed gas flow Temperature: Stepwise raised; 100°C x 2 hrs → 250°C x 2 hrs → 320°C x 2 hrs. After 100 hours' reaction, the sulfur contents of the feedstock and the product oil were measured, which were substituted into equation (1) shown below to obtain a rate constant. The relative rate constant of each catalyst, assuming the rate constant of catalyst M as a standard (100), is shown as upper figure in Tables 3 and 4, and the sulfur content (ppm by weight) in the product oil is shown as lower figure in the tables (hereinafter the same). k = LHSV n-1 x [(1/S P ) n-1 - (1/S F ) n-1 ] wherein k: reaction rate constant; n: reaction order S F : sulfur content in hydrocarbon feedstock S P : sulfur content in product oil Catalyst LHSV (hr -1 ) Example No. 1.5 4.2 A 146 120 1 219 1021 B 132 106 2 242 1150 C 130 104 3 246 1171 D 138 114 4 232 1072 E 140 116 5 228 1054 F 150 124 6 213 989 G 148 120 7 216 1021 H 140 114 8 228 1072 I 130 106 9 246 1150 J 144 116 10 222 1054 K 140 110 11 228 1120 L 152 124 12 209 989 A1 150 121 14 213 1024 Catalyst LHSV (hr -1 ) Compara. Example No. 1.5 4.2 M 100 100 1 319 1215 N 118 104 2 271 1171 O 117 106 3 273 1150 P 97 82 4 329 1468 R 120 112 6 266 1091 S 116 108 7 276 1132 EXAMPLE 14 A first impregnating solution was prepared by dissolving 38 g of phosphomolybdic acid [H 3 (PMo 12 O 40 )·30H 2 O] and 4 g of phosphoric acid in 75 g of water in an Erlenmeyer flask with stirring at room temperature. The solution was infiltrated into 100 g of an alumina carrier containing 5% of HY type zeolite (specific surface area: 372 m 2 /g; pore volume: 0.65 cc/g; substantially made of γ-alumina) in an egg-plant type flask at room temperature for 1 hour. The impregnated carrier was air dried and calcined at 500°C for 4 hours in a muffle furnace. Separately, 26.9 g of cobalt nitrate was dissolved in 60 g of water with stirring at room temperature in an Erlenmeyer flask to prepare a second impregnating solution. The above obtained catalyst was impregnated with the second impregnating solution at room temperature for 1 hour in an egg-plant type flask, air dried, and calcined at 500°C for 4 hours in a muffle furnace to obtain catalyst A1. EXAMPLE 15 Hydrodesulfurization of gas oil was carried out under the same conditions as in Example 13, except for using a γ-alumina catalyst (catalyst B1) having a specific surface area of 372 m 2 /g, a pore volume of 0.65 cc/g, an HY type zeolite content of 5%, having supported thereon Co, Mo, and P in an amount of 5%, 20% and 3%, respectively, in terms of oxide, and treating gas oil at a temperature of 320°C or 350°C at a liquid hourly space velocity of 1.5. The HY type zeolite used had an SiO 2 /Al 2 O 3 molar ratio of 6, an Na 2 O content of not more than 0.3%, a specific surface area of 970 m 2 /g as measured by a Langmuir method or 620 m 2 /g as measured by a BET method, a crystal size of from 0.7 to 1.0 micron, and a unit cell dimension of 24.45 Å. EXAMPLE 16 Hydrodesulfurization of gas oil was carried out in the same manner as in Example 15, except that the phosphorus content of the catalyst was 7%. The catalyst used here is designated catalyst C1. EXAMPLE 17 Hydrodesulfurization of gas oil was carried out in the same manner as in Example 15, except for using a γ-alumina carrier having a specific surface area of 387 m 2 /g, a pore volume of 0.65 cc/g, and an HY type zeolite content of 10%. The catalyst used here is designated catalyst D1. EXAMPLE 18 Hydrodesulfurization of gas oil was carried out in the same manner as in Example 15, except for using a γ-alumina carrier having a specific surface area of 403 m 2 /g, a pore volume of 0.65 cc/g, and an HY type zeolite content of 20%. The catalyst used here is designated catalyst E1. EXAMPLE 19 Hydrodesulfurization of gas oil was carried out in the same manner as in Example 15, except that the carrier had a specific surface area of 386 m 2 /g and a pore volume of 0.67 cc/g and consisted of an HY type zeolite which had an SiO 2 /Al 2 O 3 molar ratio of 5.5, an Na 2 O content of not more than 0.3%, a specific surface area of 730 m 2 /g as measured by a Langmuir method or 530 m 2 /g as measured by a BET method, a crystal size of from 0.6 to 0.9 micron, and a unit cell dimension of 24.55 Å. The catalyst used here is designated catalyst F1. COMPARATIVE EXAMPLE 9 Hydrodesulfurization of gas oil was carried out in the same manner as in Example 15, except that the catalyst used here (designated catalyst G1) comprised a carrier solely consisting of γ-alumina having a specific surface area of 336 m 2 /g and a pore volume of 0.71 cc/g and having supported thereon no phosphorus component. COMPARATIVE EXAMPLE 10 Hydrodesulfurization of gas oil was carried out in the same manner as in Comparative Example 9, except that the catalyst further contained 3% of phosphorus. The catalyst used here is designated catalyst H1. COMPARATIVE EXAMPLE 11 Hydrodesulfurization of gas oil was carried out in the same manner as in Example 15, except that the catalyst used (designated catalyst I1) had supported thereon no phosphorus component. COMPARATIVE EXAMPLE 12 Hydrodesulfurization of gas oil was carried out in the same manner as in Example 15, except that the carrier used in the catalyst had a specific surface area of 374 m 2 /g and a pore volume of 0.69 cc/g and consisted of the zeolite having an SiO 2 /Al 2 O 3 molar ratio of 10, an Na 2 O content of not more than 0.3%, a specific surface area of 950 m 2 /g as measured by a Langmuir method or 610 m 2 /g as measured by a BET method, a crystal size of from 0.6 to 0.9 micron, and a unit cell dimension of 24.38 Å. The catalyst used here is designated catalyst J1. COMPARATIVE EXAMPLE 13 Hydrodesulfurization of gas oil was carried out in the same manner as in Example 15, except that the catalyst used (designated catalyst K1) was different from that used in Example 1 only in mean pore diameter. COMPARATIVE EXAMPLE 14 Hydrodesulfurization of gas oil was carried out in the same manner as in Example 15, except that the catalyst used here (designated catalyst L1) was different from that used in Example 1 only in pore size distribution. The composition and physical properties of catalysts B1 to L1 obtained in Examples 15 to 19 and Comparative Examples 9 to 14 are tabulated in Table 5 below. Each of catalysts B1 to L1 was evaluated in the same manner as in Example 13, except that the reaction conditions were changed as shown in Table 6 below. The results obtained are also shown in Table 6. In the Table, the upper figures are relative activity value, assuming the rate constant of catalyst G1 of Comparative Example 9 as a standard (100), and the lower figures are sulfur contents (ppm by weight) in the product oils. Catalyst Reaction Conditions Example No. 320°C, LHSV: 1.5hr -1 340°C, LHSV: 4.2hr -1 350°C LHSV: 1.5hr -1 Example B1 136 123 153 15 370 900 140 C1 121 114 142 16 450 1000 160 D1 121 115 146 17 450 1000 150 E1 132 116 147 18 380 930 150 F1 132 116 147 19 380 930 150 G1 100 100 100 Compara. Example 610 1220 310 9 H1 102 110 115 10 540 1140 230 I1 106 97 119 11 560 1270 220 J1 113 120 124 12 520 910 210 K1 111 123 102 13 520 900 290 L1 108 117 114 14 530 920 240 The product oils obtained in Example 15 and Comparative Example 9 were analyzed with Gas Chromatograph equipped with Atomic Emission Detector, and the residual sulfur contents were determined. The results obtained are shown in Table 7. Sulfur Content (ppm by wt.) DBT 4M-DBT 4,6DM-DBT Feedstock 464 221 253 Product Oil: 340°C, LHSV=4.2 hr -1 : Example 15 41 75 107 Comparative 44 104 204 Example 9 350°C, LHSV=1.5 hr -1 : Example 15 11 11 17 Comparative 10 29 41 Example 9 As described and demonstrated above, since the catalyst used in the present invention contains both phosphorus and zeolite to a large extent, it exhibits very high desulfurization activity and is sufficiently effective on removal of such intractable substances as 4M-DBT and 4,6DM-DBT that have caused problems in the production of gas oil having a sulfur content of not more than 0.05% by weight. Thus, the present invention makes it possible to produce gas oil having an extremely reduced sulfur content.

Claims: A process for producing a catalyst for hydrodesulfurization of hydrocarbon oils comprising impregnating an inorganic oxide carrier containing a crystalline aluminosilicate with an impregnating solution consisting of a polyacid salt of a metal belonging to Group VIB of the Periodic Table, a salt of a metal belonging to Group VIII of the Periodic Table, and phosphoric acid to provide a Group VIB metal content of from 10 to 30% by weight, a Group VIII metal content of from 1 to 15% by weight, and a phosphorus content of from 0.1 to 15% by weight each in terms of oxide with respect to the total catalyst, drying the impregnated carrier, and calcining said carrier, wherein said inorganic oxide is selected from silica, alumina, boria, magnesia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-boria, alumina-zirconia, alumina-titania, alumina-boria, alumina-chromia, titania-zirconia, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, silica-magnesia-zirconia and combinations of two or more thereof. A process according to claim 1 wherein said impregnating solution is prepared at a temperature higher than 0°C and lower than 100°C. A process for producing a catalyst for hydrodesulfurization of hydrocarbon oils comprising impregnating an inorganic oxide carrier containing a crystalline aluminosilicate and being defined as in claim 1 with a first impregnating solution consisting of a polyacid salt of a metal belonging to Group VIB of the Periodic Table and phosphoric acid to provide a Group VIB metal content of from 10 to 30% by weight and a phosphorus content of from 0.1 to 15% by weight each in terms of oxide based on the total catalyst, drying the impregnated carrier, calcining said carrier, then impregnating the resulting catalyst precursor with a second impregnating solution consisting of a salt of a metal belonging to Group VIII of the Periodic Table to provide a Group VIII metal content of from 1 to 15% by weight in terms of oxide with respect to the total catalyst, drying the impregnated carrier, and calcining said carrier. A process according to claim 3 wherein said impregnating solution is prepared at a temperature higher than 0°C and lower than 100°C.

Inventors: CHIYODA OSAMU, FUJIKAWA TAKASHI, IDEI KAZUO, KITADA SHUNJI, OHKI KATSUYOSHI, SUZUKI ETSUO, USUI KAZUSHI, YAMAZAKI HATSUTARO, YUMOTO MITSUGU, CHIYODA, OSAMU, FUJIKAWA, TAKASHI, IDEI, KAZUO, KITADA, SHUNJI, OHKI, KATSUYOSHI, SUZUKI, ETSUO, USUI, KAZUSHI, YAMAZAKI, HATSUTARO, YUMOTO, MITSUGU, CHIYODA, OSAMU, C/O COSMO RES. INST., RES. AND, FUJIKAWA, TAKASHI, C/O COSMO RES. INST., RES. AND, IDEI, KAZUO, C/O COSMO RES. INST., RES. AND, KITADA, SHUNJI, C/O COSMO RES. INS., RES. AND, OHKI, KATSUYOSHI, C/O COSMO RES. INST., RES. AND, SUZUKI, ETSUO, C/O COSMO RES. INST., RES. AND, USUI, KAZUSHI, C/O COSMO RES. INST., RES. AND, YAMAZAKI, HATSUTARO, C/O COSMO RES. INS., RES. AND, YUMOTO, MITSUGU, C/O COSMO RES. INST., RES. AND
Applicants: COSMO OIL CO LTD, PETROLEUM ENERGY CENTER FOUND, COSMO OIL COMPANY, LTD, PETROLEUM ENERGY CENTER
Application year: 1994
Main classification: C10G45
IPC codes: B01J29, C10G45